KR101530836B1 - Method for preparation of imidodisulfuryl compounds - Google Patents

Abstract

The present invention relates to a process for preparing an imidosulfuryl compound in a continuous reaction at an elevated temperature.

Description

METHOD FOR PREPARATION OF IMIDODISULFURY COMPOUNDS [0002]

The present invention relates to a process for preparing an imidosulfuryl compound in a continuous reaction at an elevated temperature.

In the following, the following meanings are used unless otherwise stated:

CSI Chlorosulfonyl isocyanate

CSOS chlorosulfonic acid

ClSI bis (chlorosulfonyl) -imide

FSI fluorosulfonyl isocyanate

FSOS fluorosulfonic acid

FR flow rate

RT room temperature

Imidosulfuryl compounds are also used for a variety of purposes. One example is the use of imido disulfuryl chloride for the production of lithium bis (fluorosulfonyl) imide, which can be used in automotive batteries, for example, used as an electrolyte, such as in lithium ion batteries, and as an antistatic agent in touch screens .

DE 1 159 410 B discloses a process for preparing a halosulfonyl isocyanate by reaction of urea with a halosulfonic acid. The reaction is preferably carried out at a temperature of from 100 to 180 캜. Specifically disclosed is the preparation of chlorosulfonyl isocyanate at temperatures between 120 and 150 < 0 > C.

DE 1 143 495 B discloses a process for the preparation of imido-bis (sulfuryl) fluoride by reaction of urea with fluorosulfonic acid. The reaction temperature is initiated at room temperature unless explicitly indicated and the reaction mixture is occasionally cooled during the reaction.

CA 710255 A discloses a process for the preparation of imido-bis (sulfuryl chloride) by reaction of trichlorophosphazo-sulfuryl chloride with chlorosulfonic acid. The method as disclosed in CA 710255 has a drawback that it requires chemicals that are somewhat more expensive and have environmental drawbacks in use.

WO 2009/123328 A1 discloses the preparation of ClSI by the placement method described above in the Example section of the invention.

Imidosulfur halide (also referred to as imidobis (sulfuryl halide), imidobisulfuryl halide or bis (halidosulfonyl) imide, which may be applied to similar compounds of the invention). The scheme is shown in Scheme 1:

Scheme 1

(Wherein Xa and Xb are halogen).

Both the starting compounds, isocyanates and sulfonic acids, and the products, bisimides, are toxic and corrosive. When Xa and Xb are Cl, the product exhibits a very high pyrolytic decomposition at elevated temperatures, which requires providing a sufficient stability measure in manufacture. The heat of the reaction delta H is about 100 kJ / mol, the onset of the decomposition of the already purified furyl chloride is about 180 ° C, and the adiabatic temperature is also raised to a temperature exceeding 400 ° C. The reaction of FSOS with CSI and the reaction of CSOS with FSI shows a temperature similar to the decomposition starting temperature.

Thus, in production the reaction temperature in the batch process does not exceed 150 ° C to avoid explosion hazards. The reaction time of the batch process ranges from about 8 h to 24 h.

While isocyanates and sulfonic acids only react at elevated temperatures. Considering the environment and safety, in the past, the disulfuryl halide has already been prepared only in a small batch and at a temperature below the decomposition initiation temperature as mentioned above, resulting in the above-mentioned long reaction time.

There is a need for a process for the preparation of imidodisulfur halide having a short reaction time and a high yield without requiring the use of a phosphorus-containing chemical, wherein the product exhibits high purity and the handling of the substance and the reaction is safe and permits mass production.

Unexpectedly, it is possible to react halosulfonyl isocyanate with halosulfonic acid at a temperature above the decomposition initiation temperature of the reaction product (imidosulfuryl halide), and it is possible to obtain a high yield without the expected decomposition of the desired imidosulfuryl halide Do. It was possible to perform the reaction in an unexpected, safe manner. This allowed the desired short reaction time.

In addition, a short reaction time can realize a high purity product that does not exhibit a polymerization reaction or decomposition due to decomposition, which usually occurs at too high a temperature.

Summary of the Invention

A subject of the present invention is a process for the preparation of a compound of formula (I)

The method comprises three successive steps: StepS1, StepS2, and StepS3;

StepS1 comprises the reaction ReacS1;

Reaction (ReacS1) is the reaction of a compound of formula (III) with a compound of formula (II)

[Wherein,

X1 and X2 are the same or different and are independently selected from the group consisting of F, Cl, Br, J, _C1-6 perfluoroalkyl, and tolyl;

,

,

,

, [N(R20)(R21)(R22)R23]⁺, 및 [P(R20)(R21)(R22)R23]⁺ 로 구성된 군에서 선택되고;R ^{n +} is ^{H +, Li +, Na +} , K +, Mg 2+, Ca 2+, Zn 2+, Cu 2+, Al 3+, Ti 3+, Fe 2+, Fe 3+, B 3+ ,

,

,

,

, [N (R20) (R21) (R22) R23] ⁺ , and [P (R20) (R21) (R22) R23] ⁺ ;

R20, R21, R22 and R23 are the same or different and are independently selected from the group consisting of H, _C1-8 alkyl, _C5-6 cycloalkyl, phenyl, benzyl, vinyl and allyl;

n is 1, 2 or 3;

The reaction (ReacS1) is carried out in a continuous manner;

The mixture of the compound of formula (II) and the compound of formula (III) is passed through the device DevS1 in step S1 and the device DevS1 is a continuous working device, Wherein the mixture of the compound of formula (III) and the compound of formula (III) is heated to a temperature (TempS1) and the temperature (TempS1) is from 180 to 300 ° C,

The reaction mixture from the device DevS1 in the step (Step S2) passes through the device DevS2, and the device DevS2 is the device which cools the reaction mixture;

The reaction mixture from the device DevS2 in the step (Step S3) passes through the device DevS3, the device DevS3 is the backpressure regulating device;

The reaction mixture is cooled to the temperature (TempS2) by the influence of the combination of the device (DevS2) or the device (DevS3) or the device DevS2 and the device DevS3 at the temperature (TempS2), and the temperature (TempS2) .

Preferably, the method further comprises a step (StepS4), which is carried out after the step (Step S3), wherein the reaction mixture from the device DevS3 in the step (Step S4) is passed through the device DevS4 , And the device DevS4 is a device for separating CO ₂ from the reaction mixture.

Preferably, X1 and X2 are the same and are selected from the group consisting of F, Cl, Br, _C1-6 perfluoroalkyl and tolyl;

More preferably, X 1 and X 2 are the same and are selected from the group consisting of F, Cl and C _1-6 perfluoroalkyl;

Even more preferably, X1 and X2 are the same and selected from the group consisting of F, Cl and CF _3;

In particular, X1 and X2 are identical, Cl or CF ₃ and;

More particularly, X1 and X2 are Cl.

Preferably,

,

, [N(R20)(R21)(R22)R23]⁺ 로 구성된 군에서 선택되고;R ^{n +} is H ⁺ , Li ⁺ , Na ⁺ , K ⁺

,

, [N (R20) (R21) (R22) R23] ⁺ ;

R20, R21, R22 and R23 are the same or different and are independently selected from the group consisting of H, _C1-8 alkyl, _C5-6 cycloalkyl, phenyl, benzyl, vinyl and allyl;

More preferably,

, [N(R20)(R21)(R22)R23]⁺ 로 구성된 군에서 선택되고;R ^{n +} is H ⁺ , Li ⁺ , Na ⁺ , K ⁺

, [N (R20) (R21) (R22) R23] ⁺ ;

R20, R21, R22 and R23 are the same or different and are independently selected from the group consisting of H, _C1-8 alkyl, _C5-6 cycloalkyl, phenyl and benzyl;

Even more preferably,

, [N(R20)(R21)(R22)R23]⁺ 로 구성된 군에서 선택되고;R ^{n +} is H ⁺ , Li ⁺ , Na ⁺ , K ⁺

, [N (R20) (R21) (R22) R23] ⁺ ;

R20, R21, R22 and R23 are the same or different and are independently selected from the group consisting of H, _C1-8 alkyl, _C5-6 cycloalkyl, phenyl and benzyl;

Especially,

[N(R20)(R21)(R22)R23]⁺ 로 구성된 군에서 선택되고;R ^{n +} is H ⁺ , Li ⁺ , Na ⁺ , K ⁺

[N (R20) (R21) (R22) R23] ⁺ ;

R20, R21, R22 and R23 are the same or different and are independently selected from the group consisting of H, _C1-8 alkyl, _C5-6 cycloalkyl, phenyl and benzyl;

More particularly,

로 구성된 군에서 선택되고;R ^{n +} is H ⁺ , Li ⁺ , Na ⁺ , K ^+, and

≪ / RTI >

R20 and R21 are the same or different and are independently selected from the group consisting of H and _C1-8 alkyl;

Even more particularly,

로 구성된 군에서 선택되고;R ^{n +} is H ⁺ , Na ⁺ and

≪ / RTI >

R20 and R21 are the same or different and independently of one another are C _1-8 alkyl;

Especially,

이고, R ^{n +} H ⁺ or

ego,

R20 and R21 are the same or different and independently of one another are C _1-4 alkyl;

More particularly,

이고,R ^{n +} is H ⁺ or

ego,

R20 and R21 are the same or different and are independently selected from the group consisting of methyl, ethyl and n-butyl.

When R ^{n +} is H ⁺ , the compound of formula (III) can be represented in a conventional (conventional) manner, i.e. as a compound of formula (IIIconv)

.

.

Preferably, the reaction (ReacSl) is carried out in a tubular reactor. During passage through the device DevS1, the initially supplied mixture is gradually converted to the reaction mixture by reaction.

Preferably, the device DevS1 is selected from the group consisting of a tubular, a microreactor, a shell and tube heat exchanger, a plate heat exchanger and any conventional device for exchanging heat from the mixture;

More preferably it is tubular;

Even more preferably, it is a coil tube.

Preferably, the device DevS2 is selected from the group consisting of tubes, microreactors, shell and tube heat exchangers, plate heat exchangers and any conventional devices for exchanging heat from the reaction mixture;

More preferably this is a tube;

Even more preferably, it is a coil tube.

In particular, the devices DevS1 and DevS2 are coil tubes.

Preferably, the device DevS3 is a conventional backpressure regulator.

Preferably, the device (DevS4) is any known device suitable for this purpose that may be used in the device for releasing the gaseous CO ₂ from the liquid, the object, more preferably the device (DevS4) is a column or popsicles Ron.

Heating in the device DevS1 may be performed by any known means, preferably by means of electrical heating or by heating with a fluids heat carrier.

Cooling in the device DevS2 may be performed by any known means, preferably by means of a fluid cooling medium.

Depending on the scale of the reaction and depending on the scale of the device on which the process is carried out, the cooling of the reaction mixture can be effected not only by the influence of the device DevS2 on the reaction mixture (i. E. Pass) and also by the influence of the reaction mixture of the device DevS3 (i.e. through the device DevS3 contributing to cooling). This applies in particular when the scale of the reaction is rather small (for example when the process is carried out on a laboratory scale), whereas if the process is carried out on a production scale, cooling is preferentially performed during passage through the device DevS2 Will be.

In another embodiment, especially on a production scale, cooling can also be achieved by pressure release and expansion, which is effected by the device DevS3.

It is also possible to combine cooling by expansion, which is effected by device DevS3, and cooling during passage through device DevS2.

Preferably, the heating in the device DevS1 and the cooling in the device DevS2 are carried out in the form of a tube-in-tube set-up, in the form of a tube-in-container set-up, in the form of a shell and tube heat exchanger, In the form of any conventional apparatus for the purpose of exchanging heat from the mixture or reaction mixture;

More preferably, the heating in the device DevS1 and the cooling in the device DevS2 are realized in the form of a tube-in-tube set-up or a tube-in-container set-up.

The reaction ReacS1 is triggered in the device DevS1 by heating to the temperature of the mixture (TempS1) in the device DevS1.

The reaction ReacS1 is quenched in the device DevS2, which is performed by cooling the reaction mixture in the device DevS2 to the temperature TemS2.

Preferably, the temperature (TempS1) is 190 to 280 占 폚, more preferably 200 to 260 占 폚, even more preferably 210 to 255 占 폚, particularly 220 to 255 占 폚.

Preferably, the temperature (TempS2) is from 10 to 120 占 폚, more preferably from 15 to 100 占 폚, even more preferably from 15 to 90 占 폚, especially from 15 to 85 占 폚, more particularly from 20 to 85 占 폚.

The melting point of pure ClSI is about 35 占 폚 and therefore the lowest possible temperature value of temperature TempS2 is governed by the conversion of the reaction because the compound of formula (II) remaining in the reaction mixture and the remaining compound of formula Since the compound naturally lowers the melting point of the reaction mixture after the reaction, which lowers the temperature (TempS2) value.

Reaction (ReacS1) is performed at pressure (PressS1). Preferably, the pressure (PressS1) is between 10 and 1000 bar, more preferably between 20 and 600 bar, even more preferably between 50 and 500 bar, especially between 60 and 400 bar, more particularly between 65 and 300 bar, 200 bar, in particular 65 to 150 bar.

The pressure (PressS1) in the device DevS1 and the device DevS2 is controlled and maintained by the device DevS3.

The time (TimeS1) is the time when the mixture is exposed to the temperature (TempS1) in the device DevS1 and heated to this temperature. The reaction (ReacS1) occurs during the time (TimeS1). The time TimeS1 is thus the residence time and is preferably the residence time of the mixture in the device DevS1.

Preferably, the time (TimeS1) is from 0.5 sec to 4 h, more preferably from 1 sec to 2 h, even more preferably from 1 min to 1 h, especially from 2 min to 30 min, more particularly from 2 min to 20 min , Even more particularly from 3 min to 17 min.

The time (TimeS2) is the time at which the reaction mixture cools to the temperature (TempS2). The cooling can be performed by the action of the device DevS2, by the action of the device DevS3, or by the action of the devices DevS2 and DevS3. Cooling quenched the reaction. The time TimeS2 is thus the residence time and is preferably the residence time of the reaction mixture in the device DevS2 and in the device DevS3.

Preferably, the time (TimeS2) is 0.1 sec to 2 h, more preferably 0.5 sec to 1 h, even more preferably 1 sec to 30 min, particularly 10 sec to 30 min, more particularly 25 sec to 25 min , Even more particularly from 1 min to 25 min.

Preferably, the time (TimeS2) is 0.0001 to 0.5 times, more preferably 0.001 to 0.3 times the time (TimeS1).

Preferably, the molar amount of the compound of formula (III) is 0.5 to 1.5 times, more preferably 0.75 to 1.25, and even more preferably 0.85 to 1.15 times the molar amount of the compound of formula (II).

The compound of formula (II) and the compound of formula (III) may be fed to the device DevS1 as a premixed mixture or may be supplied separately to the device DevS1 and mixed in the device DevS1.

Any suitable mixing equipment can be used in the device DevS1 or previously for mixing purposes, which may be anything known in the art, for example a conventional branch connection, for example a T or Y piece, Mixing device.

Preferably heating from the device DevS1 to temperature TempS1 is carried out only after the compound of formula (II) and the compound of formula (III) are present as a mixture in the device DevS1.

The supply of the compound of formula (II) and the compound of formula (III) (separately or in the form of a mixture) is carried out by a device (DevS0).

Apparatus DevS0 is a pressurizing device commonly used to move fluids against pressure and is, for example, a pump. When the compound of formula (II) and the compound of formula (III) are supplied separately to device DevS1, preferably device DevS0 has a respective device for each compound.

Preferably, the devices DevS1 and DevS2 are connected to each other at the permanent fluids during operation and both are under pressure (PressS1).

Preferably, the device DevS0 is a device for augmenting the pressure (PressS1) in the device DevS1 and in a device DevS2 against the device DevS3 this is necessary for carrying out the reaction (ReacS1) at the temperature Tempsl .

More preferably, the compound of formula (II) and the compound of formula (III) are mixed under ambient pressure and ambient temperature and then fed to the device DevS1.

If the device DevS1 and / or device DevS2 is a tube, in particular a coil tube, a hotspot or a coldspot can occur despite efforts to avoid it, due to building constraints or density variations. Thus, any mentioned temperature means an average temperature in terms of hot or cold spots.

Conventional back pressure regulators that can be used for the device DevS3 operate discontinuously, i.e. by opening and closing, which release the product stream while maintaining pressure. This naturally causes a change in pressure. Therefore, the pressure (PressS1) means the average pressure.

A mixture of a compound of the formula (II) and a compound of the formula (III) and all the parts in contact with the reaction mixture are made from the respective materials, which resist the attack of the chemical under the respective conditions, i.e. stainless steel, Hastelloy, Such as Hastelloy B or Hastelloy C, titanium, tantalum, silicon carbide, silicon nitride, etc., which are also lined with materials that are passivated or inert to chemicals such as PTFE.

The compound of formula (I) can be used from an apparatus (DevS4) for any subsequent reaction without further purification, and in the case of further purification, preferably the liquid phase obtained from the apparatus (DevS4) And is preferably carried out by using a film evaporator, more preferably a wiped film evaporator.

Example

conv conversion rate is measured by measuring the content of CSI (CONT-CSI) in weight percent after the reaction in the reaction mixture using IR spectroscopy for the standard, and conv is the [100-content (CONT-CSI)] (unit: to be.

FR flow rate

nd not measured

p1 pressure (PressS1)

t1 Time (TimeS1)

t2 Time (TimeS2)

T1 temperature (TempS1)

T2 temperature (TempS2)

Examples 1 to 14

In the embodiment, equimolar premixes of CSOS and CSI were supplied to the device DevS1.

The examples were carried out using the following apparatus:

장치 (DevS0): 피스톤 펌프 260D (ISCO Teledyne 사제)

Device (DevS0): piston pump 260D (manufactured by ISCO Teledyne)

장치 (DevS1) 는 하스텔로이 C 로 제조된 내부 체적 VolS1 인 1/8 인치 코일 튜브임. 가열에 대해서는 코일-튜브-인-콘테이너 셋업을 사용하였다. 가열 매질은 통상적인 오일이였다.

The device (DevS1) is an 1/8 inch coil tube with internal volume VolS1 manufactured by Hastelloy C. For heating, a coil-tube-in-container setup was used. The heating medium was conventional oil.

장치 Dev(S2) 는 하스텔로이 C 로 제조된 약 1.5 mL 의 내부 체적의 1/8 인치 튜브임. 냉각은 실온의 룸 공기와 튜브를 단순히 접촉시킴으로써 냉각을 실시하였다.

Apparatus Dev (S2) is a 1/8 inch tube of about 1.5 mL internal volume made with Hastelloy C. Cooling was performed by simply contacting the room with room temperature air at a temperature.

장치 (DevS3): 표준 배압 조절기 (Swagelok 의 KPB 시리즈)

Device (DevS3): Standard Back Pressure Regulator (Swagelok's KPB series)

장치 (DevS4): CO₂ 를 개방 글래스 플라스크에서 반응 혼합물로부터 분리시켰다.

Device (DevS4): subsequent cleavage of the CO ₂ from the reaction mixture in an open glass flasks.

The ClSI obtained in each example was colorless to yellow liquid.

The structure was confirmed by IR spectroscopy:

IR (ATR, 24 scans, v (cm -1)): 3205 (m), 2758 (w), 2652 (w), 1727 (w), 1416 (s), 1318 1206 (m), 1167 (s), 862 (s), 567 (s), 500 (s)

Examples 15 to 17

In the embodiment, the CSOS and the CSI were separately supplied to the device DevS1 and mixed in the device DevS1 by an inline fixed mixing device.

The examples were carried out using the following apparatus:

장치 (DevS0): 피스톤 펌프 260D (ISCO Teledyne 사제)

Device (DevS0): piston pump 260D (manufactured by ISCO Teledyne)

장치 (DevS1) 는 하스텔로이 C 로 제조된 내부 체적 VolS1 인 1/8 인치 코일 튜브임. 가열에 대해서는 코일-튜브-인-콘테이너 셋업을 사용하였다. 가열 매질은 통상적인 오일이였다.

The device (DevS1) is an 1/8 inch coil tube with internal volume VolS1 manufactured by Hastelloy C. For heating, a coil-tube-in-container setup was used. The heating medium was conventional oil.

장치 Dev(S2) 는 하스텔로이 C 로 제조된 약 1.5 mL 의 내부 체적의 1/8 인치 튜브임. 실온의 룸 공기와 튜브를 단순히 접촉시킴으로써 냉각을 실시하였다.

Apparatus Dev (S2) is a 1/8 inch tube of about 1.5 mL internal volume made with Hastelloy C. Cooling was performed by simply contacting the room with room temperature air at a temperature.

장치 (DevS3): 표준 배압 조절기 (Swagelok 의 KPB 시리즈)

Device (DevS3): Standard Back Pressure Regulator (Swagelok's KPB series)

장치 (DevS4): CO₂ 를 개방 글래스 플라스크에서 반응 혼합물로부터 분리시켰다.

Device (DevS4): subsequent cleavage of the CO ₂ from the reaction mixture in an open glass flasks.

The ClSI obtained in each example was colorless to yellow liquid.

The structure was confirmed by IR spectroscopy, and the data are as shown in Examples 1 to 14.

Examples 18 to 21

In the embodiment, equimolar premix CSOS and CSI were supplied to the device DevS1.

The examples were carried out using the following apparatus:

장치 (DevS0): 피스톤 펌프 260D (ISCO Teledyne 사제)

Device (DevS0): piston pump 260D (manufactured by ISCO Teledyne)

장치 (DevS1) 는 하스텔로이 C 로 제조된 약 54 ml 의 내부 체적의 1/4 인치 코일 튜브임. 가열에 대해서는 코일-튜브-인-콘테이너 셋업을 사용하였다. 가열 매질은 통상적인 오일이였다.

The device (DevS1) is a 1/4 inch coil tube of about 54 ml internal volume made of Hastelloy C. For heating, a coil-tube-in-container setup was used. The heating medium was conventional oil.

장치 Dev(S2) 는 하스텔로이 C 로 제조된 약 15 mL 의 내부 체적의 1/8 인치 튜브임. 상이한 온도 수준 T2 에서 물과 튜브를 단순히 접촉시킴으로써 냉각을 실시하였다.

Device Dev (S2) is a 1/8 inch tube of internal volume of about 15 mL made with Hastelloy C. Cooling was performed by simply contacting the tube with water at different temperature levels T2.

장치 (DevS3): 표준 배압 조절기 (Swagelok 의 KPB 시리즈)

Device (DevS3): Standard Back Pressure Regulator (Swagelok's KPB series)

장치 (DevS4): CO₂ 를 개방 글래스 플라스크에서 반응 혼합물로부터 분리시켰다.

Device (DevS4): subsequent cleavage of the CO ₂ from the reaction mixture in an open glass flasks.

The ClSI obtained in each example was colorless to yellow liquid.

The structure was confirmed by IR spectroscopy, and the data are as shown in Examples 1 to 14.

Comparative Example

Due to the onset of decomposition, batch reactions were not allowed at temperatures above 160 ° C (for comparison with the continuous reaction of the present invention). The risk of explosion was too high. Thus, only the placement reaction at 150 ° C was allowed due to safety constraints.

An equimolar amount of CSI was added to the CSOS over a 3 hour period at 120 < 0 > C, then the mixture was heated to 150 < 0 > C for 3 hours and stirred at 150 < 0 > C for 7 hours. The conversion rate was only 90%.

Thus, the total reaction time to 90% conversion was 13 hours. The color was yellow.

Darker colors than yellow should be avoided under all circumstances in the batch process because it is an indicator of significant degradation and is also an indicator of the proximity of the explosion.

WO 2009/123328 A1 discloses the preparation of ClSI in a batch process in Synthesis Example 2. [ CSI was added to CSOS at 120 < 0 > C for 2 h, and then the mixture was stirred at 150 < 0 > C for 6 h. The yield was 65.6%.

Example 22

The equimolar premix CSOS and CSI were supplied to the device DevS1.

The examples were carried out using the following apparatus:

장치 (DevS0): 시판 피스톤 펌프

Device (DevS0): Commercial piston pump

장치 (DevS1) 는 하스텔로이 C 로 제조된 약 1200 ml 의 내부 체적의 1/2 인치 코일 튜브임. 가열에 대해서는 자켓 가열을 사용하였다. 가열 매질은 통상적인 오일이였다.

The device (DevS1) is a 1/2 inch coil tube of about 1200 ml internal volume made of Hastelloy C. For heating, jacket heating was used. The heating medium was conventional oil.

장치 Dev(S2) 는 하스텔로이 C 로 제조된 약 200 mL 의 내부 체적의 1/4 인치 튜브임. 냉각에 대해서는 자켓 냉각을 사용하였다. 냉각 매질은 통상적인 오일이였다.

Device Dev (S2) is a 1/4 inch tube of about 200 mL internal volume made with Hastelloy C. Jacket cooling was used for cooling. The cooling medium was conventional oil.

장치 (DevS3): 시판 표준 배압 조절기를 사용하였다.

Apparatus (DevS3): A commercially available standard back pressure regulator was used.

장치 (DevS4): CO₂ 를 표준 분리 장치에서 분리시켰다.

Device (DevS4): subsequent cleavage of the CO ₂ in a standard separator.

The obtained ClSI was colorless to yellow liquid.

The structure was confirmed by IR spectroscopy, and the data are as shown in Examples 1 to 14.

Example 23

Equimolar premixed trifluoromethanesulfonic acid and CSI were fed to the apparatus DevS1.

The examples were carried out using the following apparatus:

장치 (DevS0): 피스톤 펌프 260D (ISCO Teledyne 사제)

Device (DevS0): piston pump 260D (manufactured by ISCO Teledyne)

장치 (DevS1) 는 하스텔로이 C 로 제조된 내부 체적 VolS1 인 1/8 인치 코일 튜브임. 가열에 대해서는 자켓 가열 셋업을 사용하였고, 가열 매질은 통상적인 오일이였다.

The device (DevS1) is an 1/8 inch coil tube with internal volume VolS1 manufactured by Hastelloy C. For heating, a jacket heating set-up was used and the heating medium was conventional oil.

장치 Dev(S2) 는 하스텔로이 C 로 제조된 약 1.5 mL 의 내부 체적의 1/8 인치 튜브임. 실온의 룸의 공기와 튜브를 단순히 접촉시킴으로써 냉각을 실행하였다.

Apparatus Dev (S2) is a 1/8 inch tube of about 1.5 mL internal volume made with Hastelloy C. Cooling was carried out by simply contacting the tube with room air at room temperature.

장치 (DevS3): 표준 배압 조절기 (Swagelok 의 KPB 시리즈)

Device (DevS3): Standard Back Pressure Regulator (Swagelok's KPB series)

장치 (DevS4): CO₂ 를 개방 글래스 플라스크에서 반응 혼합물로부터 분리시켰다.

Device (DevS4): subsequent cleavage of the CO ₂ from the reaction mixture in an open glass flasks.

The obtained compound of formula (1) was colorless to yellow liquid:

The structure was confirmed by IR and NMR spectroscopy.

IR (ATR, 24 scans, v (cm-1)): 3279 (w), 1399 (s), 1357 (s); 1176 (s) 1149 (s), 740 (s), 611 (s), 581 (s), 510 (s), 549 (s), 476 (s).

NMR (CD3CN, 400 MHz, 24 캜, ref. 1,4 difluorobenzene) 隆 = -78.75 ppm

Furthermore, the formation of the desired product by the reaction was confirmed by comparing the formation sequence obtained by the DSC measurement with the high-level calculation data.

DSC was dynamically measured at a heating rate of 0.4 캜 / min.

Turbomole: Quantum mechanical calculations were performed using the following program: TURBOMOLE V6.5 (18161), Ahlrichs, M. Baer, M. Haeser, H. Horn, and C. Koelmel, : Program system TURBOMOLE, Chem. Phys. Lett. 162: 165 (1989); And

Gaussian: Gaussian 09, Revision D.01, MJ Frisch, GW Trucks, HB Schlegel, GE Scuseria, MA Robb, JR Cheeseman, G. Scalmani, V. Barone, B. Mennucci, GA Petersson, H. Nakatsuji, M. Caricato , J. Hasegawa, M. Ishida, T. Nakajima, K. Hasegawa, K. Toyota, J. Hasegawa, J. Hasegawa, Y. Honda, O. Kitao, H. Nakai, T. Vreven, JA Montgomery, Jr., JE Peralta, F. Ogliaro, M. Bearpark, JJ Heyd, E. Brothers, KN Kudin, VN Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, JC Burant, SS Iyengar, J. Tomasi, M. Cossi, N. Rega, JM Millam, M. Klene, JE Knox, JB Cross, J. Jaramillo, R. Gomperts, RE Stratmann, O. Yazyev, AJ Austin, R. Cammi, C. Pomelli, JW Ochterski, RL Martin, K. Morokuma, VG Zakrzewski, GA Voth, P. Salvador, JJ Dannenberg, S. Dapprich, AD Daniels, O. Farkas, JB Foresman, JV Ortiz, J. Cioslowski, and DJ Fo x, Gaussian, Inc., Wallingford CT, 2009;

Using the B3LYP 6-31G method.

Examples 24 and 25

Equimolar premixed fluorosulfonic acid and CSI were supplied to the device DevS1.

The examples were carried out using the following apparatus:

장치 (DevS0): 피스톤 펌프 260D (ISCO Teledyne 사제)

Device (DevS0): piston pump 260D (manufactured by ISCO Teledyne)

장치 (DevS1) 는 하스텔로이 C 로 제조된 내부 체적 VolS1 인 1/8 인치 코일 튜브임. 가열에 대해서는 자켓 가열 셋업을 사용하였고, 가열 매질은 통상적인 오일이였다.

The device (DevS1) is an 1/8 inch coil tube with internal volume VolS1 manufactured by Hastelloy C. For heating, a jacket heating set-up was used and the heating medium was conventional oil.

장치 Dev(S2) 는 하스텔로이 C 로 제조된 약 1.5 mL 의 내부 체적의 1/8 인치 튜브임. 실온의 룸의 공기와 튜브를 단순히 접촉시킴으로써 냉각을 실행하였다.

Apparatus Dev (S2) is a 1/8 inch tube of about 1.5 mL internal volume made with Hastelloy C. Cooling was carried out by simply contacting the tube with room air at room temperature.

장치 (DevS3): 표준 배압 조절기 (Swagelok 의 KPB 시리즈)

Device (DevS3): Standard Back Pressure Regulator (Swagelok's KPB series)

장치 (DevS4): CO₂ 를 개방 글래스 플라스크에서 반응 혼합물로부터 분리시켰다.

Device (DevS4): subsequent cleavage of the CO ₂ from the reaction mixture in an open glass flasks.

The obtained compound of formula (2) was a colorless to yellow liquid:

The structure was confirmed by NMR spectroscopy:

NMR (CD3CN, 400 MHz, 24 캜, ref: benzenesulfonyl fluoride) 隆 = 57.24 ppm

Application example

The purity and yield of any of Examples 1 to 22 can be determined indirectly by using the products obtained as the respective substrates in the reaction for the preparation of bis (fluorosulfonyl) -imide. As an example for such yield and purity measurement, the product prepared according to Example 22 is hereinafter referred to as the bis [di ((fluorosulfonyl) imide] zinc salt analogously to Synthesis Example 19-1 of WO 2009/123328 A1 How it is used as a substrate for preparation is described below:

In a 500 ml reaction tube, nitrile and 20.3 g ClSI (0.093 mol, prepared according to Example 22) were charged with 179.3 g of baluler and then stirred. In the reaction tube, 10.6 g (0.10 mol) of anhydrous ZnF ₂ was added and the reaction was then carried out at room temperature (25 ° C) for 3 hours. Bis (di (fluorosulfonyl) imide] zinc salt was obtained as a solution (Yield: 66.4%, measured by ¹⁹ F-NMR and calculated on ClSI basis (100% content)).

Any products made according to Examples 1-22 of the present invention had similar purity and were obtained in a similar yield.

Example 26

Equimolar premix 1-n-Butyl-3-methylimidazolium trifluoromethanesulfonate and CSI were fed into the apparatus DevS1.

The examples were carried out using the following apparatus:

장치 (DevS0): 피스톤 펌프 260D (ISCO Teledyne 사제)

Device (DevS0): piston pump 260D (manufactured by ISCO Teledyne)

장치 (DevS1) 는 하스텔로이 C 로 제조된 내부 체적 VolS1 인 1/8 인치 코일 튜브임. 가열에 대해서는 자켓 가열 셋업을 사용하였고, 가열 매질은 통상적인 오일이였다.

The device (DevS1) is an 1/8 inch coil tube with internal volume VolS1 manufactured by Hastelloy C. For heating, a jacket heating set-up was used and the heating medium was conventional oil.

장치 Dev(S2) 는 하스텔로이 C 로 제조된 약 1.5 mL 의 내부 체적의 1/8 인치 튜브임. 실온의 룸의 공기와 튜브를 단순히 접촉시킴으로써 냉각을 실행하였다.

Apparatus Dev (S2) is a 1/8 inch tube of about 1.5 mL internal volume made with Hastelloy C. Cooling was carried out by simply contacting the tube with room air at room temperature.

장치 (DevS3): 표준 배압 조절기 (Swagelok 의 KPB 시리즈)

Device (DevS3): Standard Back Pressure Regulator (Swagelok's KPB series)

장치 (DevS4): CO₂ 를 개방 글래스 플라스크에서 반응 혼합물로부터 분리시켰다.

Device (DevS4): subsequent cleavage of the CO ₂ from the reaction mixture in an open glass flasks.

The obtained compound of formula (1) was a yellow liquid:

For the reaction products, the following analytical data were measured.

IR (ATR, 24 scans, v (cm -1)): 3122 (w), 2966 (w), 1573 (w), 1404 (w), 1353 (s), 1029 (s), 836 (m), 746 (m), 636 (s), 622 (s), 584 , 4 difluorobenzene)? = -79.28 ppm.

Claims (13)

A process for the preparation of a compound of formula (I)

The method includes three successive steps: StepS1, StepS2, and StepS3;
StepS1 comprises the reaction ReacS1;
Reaction (ReacSl) is the reaction of a compound of formula (II) with a compound of formula (III)

[Wherein,
X1 and X2 are the same or different and are independently selected from the group consisting of F, Cl, Br, J, _C1-6 perfluoroalkyl, and tolyl;
R ^{n +} is ^{H +, Li +, Na +} , K +, Mg 2+, Ca 2+, Zn 2+, Cu 2+, Al 3+, Ti 3+, Fe 2+, Fe 3+, B 3+ ,

[N (R20) (R21) (R22) R23] ⁺ , and [P (R20) (R21) (R22) R23] ⁺ ;
R20, R21, R22 and R23 are the same or different and are independently selected from the group consisting of H, _C1-8 alkyl, _C5-6 cycloalkyl, phenyl, benzyl, vinyl and allyl;
n is 1, 2 or 3;
The reaction (ReacS1) is carried out in a continuous manner;
In step S1, the mixture of the compound of formula (II) and the compound of formula (III) passes through the device DevS1, the device DevS1 is a continuous working device, The mixture of the compound and the compound of formula (III) is heated to a temperature (TempS1) (TempS1 is from 180 to 300 ° C, where the reaction (ReacS1) occurs)
The reaction mixture from the device DevS1 passes through the device DevS2 in the step S2 and the device DevS2 is the device for cooling the reaction mixture;
The reaction mixture from the device DevS2 passes through the device DevS3 in the step S13 and the device DevS3 is the device for the back pressure adjustment;
The reaction mixture is cooled to the temperature (Temps2) by the influence of the combination of the device DevS2 or DevS3 or the combination of the devices DevS2 and DevS3 on the reaction mixture and the temperature Temps2 is between 0 and 150 ° C , ≪ / RTI > 2. The method according to claim 1, wherein the further step (StepS4) is carried out after the step (StepS3), and the reaction mixture from the device DevS3 in the step (StepS4) ) passes through the apparatus (DevS4) is a method apparatus for separating CO ₂ from the reaction mixture. 3. A process according to claim 1 or 2, wherein X1 and X2 are the same and are selected from the group consisting of F, Cl, Br, _C1-6 perfluoroalkyl and tolyl. 3. The method according to claim 1 or 2,
R ^{n +} is H ⁺ , Li ⁺ , Na ⁺ , K ⁺

[N (R20) (R21) (R22) R23] ⁺ ;
R20, R21, R22 and R23 are the same or different and are independently selected from the group consisting of H, _C1-8 alkyl, _C5-6 cycloalkyl, phenyl, benzyl, vinyl and allyl. 3. The method according to claim 1 or 2, wherein the device DevS1 is selected from the group consisting of tubes, microreactors, shell and tube heat exchangers, and plate heat exchangers. 3. The method according to claim 1 or 2, wherein the device DevS2 is selected from the group consisting of tubes, microreactors, shell and tube heat exchangers, and plate heat exchangers. 3. The method according to claim 1 or 2, wherein the device DevS3 is a conventional back pressure regulator. 3. The method according to claim 1 or 2, wherein the temperature (TempS1) is 190 to 280 deg. 3. The method according to claim 1 or 2, wherein the temperature (TempS2) is 10 to 120 DEG C. 3. The process according to claim 1 or 2, wherein the reaction (ReacS1) is carried out at a pressure (PressS1) and the pressure (PressS1) is between 10 and 1000 bar. 3. The method of claim 1 or 2, wherein the time (TimeS1) is 0.5 sec to 4 h; Wherein the time (TimeS1) is the time at which the mixture is exposed to heat in the device (DevS1) and is exposed to the temperature (TempS1). 3. The method of claim 1 or 2, wherein the time (TimeS2) is 0.1 sec to 2 h; Wherein the time (TimeS2) is the time at which the reaction mixture is cooled to the temperature (TempS2). 3. The process according to claim 1 or 2, wherein the molar amount of the compound of formula (III) is 0.5 to 1.5 times the molar amount of the compound of formula (II).